CN114409905B - Acrylate modified organic silicon resin and application thereof in UV/moisture dual-curing organic silicon three-proofing paint - Google Patents
Acrylate modified organic silicon resin and application thereof in UV/moisture dual-curing organic silicon three-proofing paint Download PDFInfo
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Abstract
The invention discloses an acrylate modified organic silicon resin and application thereof in UV/moisture dual-curing organic silicon three-proofing paint. The acrylate modified organic silicon resin is used as base resin to prepare the organic silicon resin three-proofing paint with ultraviolet and moisture dual curing effects. The organic silicon resin three-proofing paint can be widely applied to bonding encapsulation of various materials, in particular to bonding encapsulation in the fields of electronic appliances, lighting lamps and the like.
Description
Technical Field
The invention belongs to the technical field of organic silicon materials, and particularly relates to an acrylate modified organic silicon resin agent and application thereof in UV/moisture dual-cured organic silicon three-proofing paint.
Background
The organic silicon polymer material has excellent high and low temperature resistance, weather resistance, aging resistance, low surface tension and physiological inertia due to unique composition and molecular structure, is widely researched and applied in the industries of aerospace, war industry, chemical engineering, transportation, building and the like, and gradually goes into daily life. Notably, silicone resins play a particularly prominent role in the electronics industry. The main reason is that functional products such as adhesives and coatings prepared from organic silicon resin have excellent functions of bonding, insulation, moisture prevention, electric leakage prevention, shock prevention, dust prevention, corrosion prevention, aging prevention, corona resistance and the like, and can be used as packaging materials of electronic components, so that circuit boards and related equipment are protected from environmental erosion, and the service stability and the service life of electronic products are improved.
However, the curing methods of the conventional silicone materials are generally as follows: thermal free radical curing by initiating polymerization of double bond groups by a peroxide initiator; carrying out thermal addition curing on double bond groups and silicon hydride under the action of a platinum catalyst; moisture curing is performed by the alkoxy group reacting with moisture in the air. However, the curing method often requires high temperature or several hours or even days to cure, which limits the application of the silicone material in some fields to a certain extent.
UV curing is a technique that, under irradiation with radiation having a certain energy, initiates rapid polymerization of unsaturated double bonds in monomers or oligomers to obtain rapid crosslinking. As early as 2004, the radiation curing international conference, uv curing technology was defined as an industrial technology with "5E" property, namely efficient, enabling, environmental, energy saving, environmental friendly. Therefore, the technology has very wide application prospect in the industrial fields of adhesives, coating, electronic packaging and the like. The method provides a brand new technical idea for the rapid curing of the organic silicon resin and the high-efficiency industrialization thereof. Currently, UV curing systems can be generally classified into radical curing systems and cationic curing systems according to the difference in curing groups. Currently, the commonly used UV curing materials are generally acrylate resins, which cure according to a free radical curing mechanism. Such resins have strong UV reactivity, can adjust viscosity and hardness according to different application conditions, and are well-established UV curing materials.
Nevertheless, the conventional acrylate-based UV curable resins still have the following drawbacks: (1) Although the traditional acrylate-based resin has very high UV reaction activity and extremely high curing rate (generally in the order of seconds), the inherent radical polymerization mechanism of the acrylate-based resin makes the acrylate-based resin very sensitive to oxygen in the environment, and the presence of the oxygen can generate obvious polymerization inhibition effect on (methyl) acrylate groups, so that the surface of the cured material is sticky; (2) Since the curing process of the uv curable resin system is initiated by uv light, the uv curing efficiency of the system will be limited by the shape, thickness, color, etc. of the cured object. For example, for a curing object with a complicated shape, a region that cannot be directly irradiated with light and a region where a shadow is formed will not achieve complete ultraviolet curing. (3) The resin also has the defects of poor high-low temperature resistance, poor aging resistance and the like, and is difficult to meet the performance requirements of some fields. Therefore, the above problems are particularly prominent in the case of uv-curable adhesives and three-proofing paints applied to bonding/packaging of electronic components. In view of the problem that the shadow area is not completely cured, the invention patent of publication No. CN102925062A provides a UV/heat dual-curing transparent resin, which solves the problem that the shadow area is not completely cured, but needs a heating process, and the production efficiency is still not improved.
Based on this, researchers provide a solution of ultraviolet-moisture dual-curing silicone resin, which can achieve rapid setting/surface drying through ultraviolet curing technology; on the other hand, moisture curing can be performed by moisture in the air, and complete curing can be achieved by solving the problem of surface stickiness due to oxygen inhibition and causing areas that cannot be cured by ultraviolet rays in areas such as shadows or underlayers. Meanwhile, the dual-curing organic silicon resin not only keeps the excellent physical and chemical properties of the traditional organic silicon material, but also realizes high-efficiency and rapid curing, and the curing process is safe, low in energy consumption and free from pollution. Greatly broadens the application field of the organic silicon resin. The invention patent of publication No. CN109370507A discloses a UV/moisture dual-curing three-proofing adhesive with low viscosity and a preparation method thereof, wherein the three-proofing adhesive can be rapidly cured under the irradiation of ultraviolet light, and the shadow part can be further and completely cured through moisture. However, the problem of oxygen inhibition is significant, and yellowing is likely to occur at high temperatures. The invention patent of publication No. CN 111040726A discloses a UV/moisture dual-curing organic silicon coating adhesive and a preparation method thereof, which can be rapidly cured and shaped under the irradiation of ultraviolet light, and further completely cured by moisture to achieve the mechanical property and the aging resistance similar to those of the traditional thermosetting organic silicon resin, but the preparation process is complex and needs to use dangerous raw materials such as concentrated sulfuric acid and the like.
The invention content is as follows:
in view of the above-mentioned shortcomings of the prior art, the present invention provides an acrylate modified silicone resin with dual curing function of ultraviolet light and moisture, and also provides a silicone resin three-proofing paint with dual curing function of ultraviolet light and moisture prepared by using the acrylate modified silicone resin as a base resin. The organic silicon resin conformal coating has high and low temperature resistance, can be rapidly cured by ultraviolet light, and can be further cured in a shadow region which cannot be irradiated by light through a two-stage moisture reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
an acrylate modified silicone resin with ultraviolet and moisture dual curing functional characteristics, which has a structural formula shown as (1):
wherein the end group R 1 is-OH, R 2 is-H; r is 3 And R 4 Are each-CH 3 or-H; r 5 And R 6 Are respectively-CH 3 、-CH 2 CH 3 、-C 6 H 5 、-CH＝CH 2 or-CH = CHCH 3 . x =0-30; y =20-1000; z =0-30; x, y and z are integers, and x and z are not 0 at the same time. The structure of the ultraviolet curing ultraviolet light-cured silicon-containing epoxy resin contains functional double bond groups and silicon hydroxyl groups, and the combination of the functional double bond groups and the silicon hydroxyl groups can realize the dual curing function of ultraviolet light and moisture.
The preparation steps of the acrylate modified organic silicon resin are as follows: hydroxyl silicone oil with double hydroxyl end capping, a silane coupling agent containing double bonds, deionized water and an organic tin catalyst are added into a three-neck flask with a stirring and condensing reflux device according to a certain proportion. Reacting under certain conditions, and sequentially carrying out extraction/centrifugation combination mode, reduced pressure purification treatment and other steps on the reaction product to obtain the target organic silicon resin product. In the reaction process, a silane coupling agent containing double bonds and water are subjected to hydrolysis reaction to generate silanol (silicon hydroxyl); then, under the action of a catalyst, the silanol and the hydroxyl silicone oil with the double hydroxyl end capping carry out polycondensation reaction. The functionality of the double bond (the functionality can be up to more than 10) can be effectively adjusted by adjusting the test conditions, and the ultraviolet curing rate and the mechanical strength of the cured product are ensured.
In the preparation method of the acrylate modified organic silicon resin, the mass ratio of the hydroxyl silicone oil with the double-bond-containing silane coupling agent is 1; the molar ratio of the deionized water to the double-bond-containing silane coupling agent is 1; the addition amount of the organotin catalyst is 0.2 to 3.0 percent of the total mass of the system; reaction conditions are as follows: the mechanical stirring speed is 300-1000 rpm, the reaction temperature is 0-50 ℃, and the reaction time is 2-24 h; the product purification extraction solvent is one or more of organic solvents such as methanol, ethanol, n-hexane and the like, the volume ratio of the extraction agent to the reaction liquid is 0.5: 1000-10000rpm for 1-50 min; vacuum oven system (30-70 deg.C, 50-500Pa, 1-24 hr) is used for vacuum purification treatment (removing small amount of extractant in the system).
Further, the structural formula of the dihydroxy terminated hydroxyl silicone oil is shown as the formula (2), and the viscosity is 50mPa.s-80000mPa.s.
Wherein R is 5 And R 6 Are respectively-CH 3 、-CH 2 CH 3 、-C 6 H 5 、-CH＝CH 2 or-CH = CHCH 3 ，n＝20-1000。
The organic tin catalyst comprises one or more of dibutyltin diethyl hexanoate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin dioctanoate, dibutyltin dimethylmaleate, dibutyltin maleate, dibutyltin dimethoxide, dioctyltin distearate, dibutyltin dimethyl, dibutyltin diphenoxy, dibutyltin diacetylacetonate, tin stearate, tin octoate, tin naphthenate, triisopropoxymonobutyltin and monobutyltin trioctoate.
The double-bond-containing silane coupling agent comprises one or more of 3-methacryloxypropyl methyldimethoxysilane, 3-acryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane and 3-acryloxypropyl methyldiethoxysilane.
Furthermore, the UV/moisture dual-curing organic silicon three-proofing paint comprises the following components in parts by mass:
acrylate-modified silicone resin: 100 parts of (A); corresponding to MA-PMPS-OH
Diluent (b): 40-100 parts;
photoinitiator (2): 1-5 parts; corresponding photoinitiators
Moisture curing accelerator: 1-30 parts;
moisture curing catalyst: 0.1 to 5 portions. Corresponding moisture sulfiding catalyst
Silane coupling agent
The diluent is selected from one or more of 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), 4-Acetoacetylmorpholine (ACMO), cyclotrimethylolpropane formal acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofuran acrylate (THFA), trimethylolpropane triacrylate (TMPTA) and neopentyl glycol diacrylate.
The photoinitiator is selected from one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), (2, 4, 6-trimethylbenzoyl chloride) diphenyl phosphine oxide (TPO), 2-dimethoxy-2-phenyl acetophenone (BDK), methyl Benzoylformate (MBF) and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819).
The moisture curing accelerator is one or more of methyltrimethoxysilane, methyltriethoxysilane, methyltributone oxime silane, methyltriacetoxysilane, 3-methacryloxypropyltri (methoxyethoxy) silane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, and tetraethyl orthosilicate. The moisture curing accelerator and the silicon hydroxyl group in the acrylate modified silicone resin structure have moisture curing reaction.
The moisture curing catalyst is one or more of dibutyltin diethyl hexanoate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin dioctanoate, dibutyltin dimethylmaleate, dibutyltin maleate, dibutyltin dimethoxide, dioctyltin distearate, dibutyltin dimethyl, dibutyltin diphenoxy, dibutyltin diacetylacetonate, tin stearate, tin octoate, tin naphthenate, triisopropoxymonobutyltin and monobutyltin trioctoate.
The curing mode of the organic silicon three-proofing paint is the synergistic effect of UV light curing and moisture curing (mainly in the area which can not be irradiated by ultraviolet light); the dual-curing organic silicon three-proofing paint is mainly used for bonding and packaging in the fields of electronic appliances (circuit boards), lighting lamps and the like.
The UV/moisture dual-curing organosilicon three-proofing paint has moderate molecular weight, can adjust viscosity according to needs, can be quickly cured under the irradiation of ultraviolet light to reach surface dryness, and can be completely cured in a moisture curing mode for shadow areas with complex shapes. The defect that the traditional organic silicon resin needs high-temperature curing is avoided. The adhesive meets the requirements of environmental protection, has good high and low temperature resistance, weather resistance, electrical insulation property, physical and mechanical properties and adhesive property, and can be widely applied to the adhesive encapsulation of various materials, in particular to the adhesive encapsulation in the fields of electronic appliances, lighting lamps and the like.
Compared with the prior art, the beneficial results of the invention are as follows:
(1) The preparation process is simple and controllable, the energy required by the reaction is low, and the method is suitable for large-scale production.
(2) Through rapid UV light curing, the defects that the traditional organic silicon resin needs high-temperature curing and the curing time is long are overcome; in addition, moisture curing can be utilized to make up the problem that ultraviolet light is difficult to quickly dry in a partial area (namely a shadow) which cannot be irradiated; the epoxy resin composition has excellent physical properties such as weather resistance, corrosion resistance, excellent mechanical properties and the like while realizing rapid curing.
(3) Compared with the traditional acrylate resin, the acrylic resin has better weather resistance and low yellowing resistance at high temperature, and simultaneously has lower VOC content.
Drawings
FIG. 1 is a reaction equation for the synthesis of acrylate-modified silicone resin in example 2.
The specific implementation mode is as follows:
the present invention is further illustrated in detail by the following examples, which are not intended to limit the scope of the present invention, and the units used are parts by mass.
Example 1:
placing dihydroxy-terminated polysiloxane and 3-methacryloxypropylmethyldimethoxysilane (the mass ratio of the two is 1. After the reaction, a certain amount of n-hexane (the volume ratio of n-hexane to the reaction solution is 1; finally, the mixture was purified in a vacuum oven (60 ℃,4 hours) to obtain an acrylate-modified silicone resin a.
Example 2:
placing dihydroxy-terminated polysiloxane and 3-acryloyloxypropylmethyldiethoxysilane (the mass ratio of the two is 4. After the reaction, a certain amount of n-hexane (n-hexane to reaction liquid volume ratio of 2; finally, the mixture was purified in a vacuum oven (50 ℃ C., 10 hours) to obtain an acrylate-modified silicone resin B.
Example 3:
placing the dihydroxy-terminated polysiloxane and 3-acryloyloxypropylmethyldimethoxysilane (the mass ratio of the two is 6. After the reaction, a certain amount of ethanol (ethanol to reaction solution volume ratio of 3; finally, purification treatment (40 ℃,18 h) was carried out in a vacuum oven to obtain an acrylate-modified silicone resin C.
Example 4:
the organic silicon three-proofing paint composition is prepared according to the following formula in parts by weight:
acrylate-modified silicone resin: 50 parts of an acrylate-modified silicone resin A; diluent (b): 25 parts of isobornyl acrylate +5 parts of hexanediol diacrylate +10 parts of tetrahydrofuran acrylate; photoinitiator (2): 1 part of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) and 1 part of (2, 4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide (TPO); moisture curing accelerator: 5 parts of tetraethyl orthosilicate; moisture curing catalyst: 0.5 part of dibutyltin dilaurate.
In addition, the invention also provides a preparation method of the ultraviolet/moisture dual-curing organic silicon three-proofing paint, which comprises the following specific steps: sequentially adding the components into a flask, and continuously mechanically stirring for 10min at the rotating speed of 800rpm to uniformly mix the components; and removing bubbles in the mixed solution by ultrasound (5 min) to obtain the organic silicon three-proofing paint.
Example 5:
the organic silicon three-proofing paint composition is prepared according to the following formula in parts by weight:
the acrylate modified organic silicon resin comprises 30 parts of acrylate modified organic silicon resin A and 30 parts of acrylate modified organic silicon resin B; diluent agent: 30 parts of isobornyl acrylate, 5 parts of hexanediol diacrylate and 15 parts of tetrahydrofuran acrylate; photoinitiator (2): 2 parts of phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819) and 1 part of Methyl Benzoylformate (MBF); moisture curing accelerator: 7 parts of methacryloxypropyltrimethoxysilane; moisture curing catalyst: 1 part of tin octoate.
The preparation method of the ultraviolet/moisture dual-curing organic silicon three-proofing paint comprises the following steps: reference is made to example 4 for a specific method of implementation.
Example 6:
the organic silicon three-proofing paint composition is prepared according to the following formula in parts by weight:
the acrylate modified silicone resin comprises 30 parts of acrylate modified silicone resin A, 20 parts of acrylate modified silicone resin B and 20 parts of acrylate modified silicone resin C; diluent agent: 25 parts of isobornyl acrylate +20 parts of trimethylolpropane triacrylate +15 parts of tetrahydrofurfuryl acrylate; photoinitiator (2): 1 part of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) and 2 parts of (2, 4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide (TPO); moisture curing accelerator: 6 parts of tetraethyl orthosilicate and 4 parts of methyltrimethoxysilane; moisture curing catalyst: 1.5 parts of monobutyltin trioctoate.
The preparation method of the ultraviolet/moisture dual-curing organic silicon three-proofing paint comprises the following steps: reference is made to example 4 for a specific method of implementation.
Example 7:
the organic silicon three-proofing paint composition is prepared according to the following formula in parts by weight:
20 parts of acrylate modified organic silicon resin A, 30 parts of acrylate modified organic silicon resin B and 30 parts of acrylate modified organic silicon resin C; diluent agent: 30 parts of isobornyl acrylate, 20 parts of trimethylolpropane triacrylate and 20 parts of tetrahydrofuran acrylate; photoinitiator (2): 4 parts of 1-hydroxycyclohexylphenylketone (184); moisture curing accelerator: 15 parts of aminopropyltriethoxysilane; moisture curing catalyst: 2.0 parts of dibutyltin dimethoxide.
The preparation method of the ultraviolet/moisture dual-curing organic silicon three-proofing paint comprises the following steps: reference is made to example 4 for a specific method of implementation.
Example 8:
the organic silicon three-proofing paint composition is prepared according to the following formula in parts by weight:
acrylate-modified silicone resin: 30 parts of acrylate modified silicone resin A +30 parts of acrylate modified silicone resin B; diluent agent: 40 parts of isobornyl acrylate, 25 parts of trimethylolpropane triacrylate and 15 parts of 4-acetoacetylmorpholine; photoinitiator (2): 3 parts of 1-hydroxycyclohexyl phenyl ketone (184) and 2 parts of 2, 2-dimethoxy-2-phenylacetophenone (BDK); moisture curing accelerator: 20 parts of 3-methacryloxypropyltris (methoxyethoxy) silane; moisture curing catalyst: 2.5 parts of dioctyltin distearate.
The preparation method of the ultraviolet/moisture dual-curing organic silicon three-proofing paint comprises the following steps: reference is made to example 4 for a specific method of implementation.
Example 9:
the organic silicon three-proofing paint composition is prepared according to the following formula in parts by weight:
acrylate-modified silicone resin: 30 parts of acrylate modified organic silicon resin A, 30 parts of acrylate modified organic silicon resin B and 30 parts of acrylate modified organic silicon resin C; diluent agent: 55 parts of isobornyl acrylate, 20 parts of tripropylene glycol diacrylate and 15 parts of tetrahydrofuran acrylate; photoinitiator (2): 2 parts of Methyl Benzoylformate (MBF) and 3 parts of (2, 4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide (TPO); moisture curing accelerator: 10 parts of 3-methacryloxypropyltris (methoxyethoxy) silane and 15 parts of acryloxypropyltriethoxysilane; moisture curing catalyst: 4.0 parts of dibutyltin dimethylmaleate.
The preparation method of the ultraviolet/moisture dual-curing organic silicon three-proofing paint comprises the following steps: reference is made to example 4 for a specific method of implementation.
Table 1 uv and moisture cure characteristics of the samples of the examples
Note:
1) In the above experimental examples, in the ultraviolet light curing test, the ultraviolet light source used LED ultraviolet lamps with a light intensity of 40mw/cm 2 。
2) Moisture curing conditions: in the dark, 20 ℃ and ambient humidity (30-55 RH%).
3) "- -" indicates no testing was performed.
TABLE 2 hardness, tensile strength and adhesion values for the samples of the examples
Note: the samples are all at 40mw/cm 2 Irradiating for 60s by using an ultraviolet lamp; curing for 48h at 25 ℃ and 50% (RH) relative humidity.
As can be seen from Table 1, the silicone three-proofing paint sample in the invention can achieve a completely surface-dry curing effect under lower energy (the light curing energy is lower than 3600 mJ/cm) 2 ). It can be seen from table 2 that better physical properties can be achieved in the cured product by adjusting the types and amounts of the various components in the silicone composition.
The above description is only exemplary for the purpose of illustrating the present invention and is not intended to limit the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of acrylate modified organic silicon resin with ultraviolet and moisture dual curing function characteristics is characterized in that the structural formula of the acrylate modified organic silicon resin with ultraviolet and moisture dual curing function characteristics is shown as (1):
wherein the terminal group R 1 is-OH, R 2 is-H; r 3 And R 4 is-CH 3 or-H; r 5 And R 6 is-CH 3 、-CH 2 CH 3 、-C 6 H 5 、-CH＝CH 2 or-CH = CHCH 3 X =0-30; y =20-1000; z =0-30; x, y and z are integers, and x and z are not 0; the preparation steps of the acrylate modified organic silicon resin are as follows: adding hydroxyl silicone oil with double hydroxyl end capping, a silane coupling agent containing double bonds, deionized water and an organic tin catalyst into a three-neck flask with a stirring and condensing reflux device according to a certain proportion, and reacting under certain conditions, wherein the reaction conditions are as follows: the mechanical stirring speed is 300-1000 rpm, the reaction temperature is 0-50 ℃, the reaction time is 2-24 h, and the reaction product is subjected to extraction/centrifugation combination mode and reduced pressure purification treatment in sequence to obtain the acrylate modified organic silicon resin;
the structural formula of the dihydroxy-terminated hydroxy silicone oil is shown as (2), the viscosity is 50mPa.s-80000mPa.s,
wherein n =20-1000, R 5 And R 6 is-CH 3 、-CH 2 CH 3 、-C 6 H 5 、-CH＝CH 2 or-CH = CHCH 3 ；
The double-bond-containing silane coupling agent is one or more of 3-methacryloxypropyl methyldimethoxysilane, 3-acryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane and 3-acryloxypropyl methyldiethoxysilane.
2. The method for preparing the acrylate modified silicone resin with ultraviolet and moisture dual curing function characteristics according to claim 1, wherein the mass ratio of the dihydroxy terminated hydroxy silicone oil to the double bond containing silane coupling agent is 1 to 1; the molar ratio of the deionized water to the silane coupling agent is 1; the addition amount of the organotin catalyst is 0.2 to 3.0 percent of the total mass of the system; the product purification extraction solvent is one or more of methanol, ethanol and n-hexane organic solvent, the volume ratio of the extraction agent to the reaction liquid is 0.5: 1000-10000rpm for 1-50 min; the vacuum oven system is adopted for decompression and purification treatment, and the drying conditions are as follows: 30-70 ℃ and 50-500Pa for 1-24 h.
3. The method for preparing the acrylate-modified silicone resin with ultraviolet and moisture dual curing functional characteristics according to claim 1, wherein the organic tin catalyst comprises one or more of dibutyltin diethyl hexanoate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin maleate, dibutyltin dimethoxide, dioctyltin distearate, dibutyltin dimethyl, dibutyltin diphenoxy, dibutyltin diacetylacetonate, tin stearate, tin octylate, and tin naphthenate, triisopropoxymonobutyltin, and monobutyltin trioctoate.
4. An acrylate-modified silicone resin having ultraviolet and moisture dual curing functional characteristics prepared by the method of any one of claims 1 to 3.
5. The UV/moisture dual-curing organic silicon three-proofing paint is characterized by being prepared from the following components in parts by mass:
the acrylate-modified silicone resin of claim 4: 100 parts of a binder;
diluent agent: 40-100 parts;
photoinitiator (2): 1-5 parts;
moisture curing accelerator: 1-30 parts;
moisture curing catalyst: 0.1 to 5 portions.
6. The UV/moisture dual-cure silicone tri-proof paint according to claim 5, wherein the diluent is selected from one or more of 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), 4-Acetoacetylmorpholine (ACMO), cyclic Trimethylolpropane Formal Acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofuran acrylate (THFA), trimethylolpropane triacrylate (TMPTA), neopentyl glycol diacrylate.
7. The UV/moisture dual-cure silicone tri-proofing paint according to claim 5, wherein the photoinitiator is selected from one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, (2, 4, 6-trimethylbenzoyl chloride) diphenyl phosphine oxide, 2-dimethoxy-2-phenyl acetophenone, methyl benzoylformate, and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
8. The UV/moisture dual-curing silicone tri-proof paint as claimed in claim 7, wherein the moisture curing accelerator is one or more of methyltrimethoxysilane, methyltriethoxysilane, methyltributone oxime silane, methyltriacetoxysilane, 3-methacryloxypropyltris (methoxyethoxy) silane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, tetraethyl orthosilicate;
the moisture curing catalyst is one or more of dibutyltin diethyl hexanoate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin dioctoate, dibutyltin dimethyl maleate, dibutyltin dimethoxide, dioctyltin distearate, dibutyltin dimethyl, dibutyltin diphenoxy, dibutyltin diacetylacetonate, tin stearate, tin octoate and tin naphthenate, triisopropoxymonobutyltin and monobutyltin trioctoate.
9. The use of a UV/moisture dual-cure silicone tri-proofing paint according to any of claims 5-8 for adhesive encapsulation.
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| CA1337224C (en) * | 1987-11-06 | 1995-10-03 | Beth I. Gutek | Compositions having uv cure with moisture shadow cure |
| JPH09151328A (en) * | 1995-11-30 | 1997-06-10 | Toray Dow Corning Silicone Co Ltd | Curing catalyst for organopolysiloxane composition and curable organopolysiloxane composition |
| US6828355B1 (en) * | 1999-07-19 | 2004-12-07 | Henkel Corporation | Resin-reinforced UV, moisture and UV/moisture dual curable silicone compositions |
| CN102408569B (en) * | 2010-09-21 | 2013-07-24 | 北京化工大学 | Dual-curable polysiloxane acrylate resin and preparation method thereof |
| CN102627943A (en) * | 2012-04-11 | 2012-08-08 | 北京化工大学常州先进材料研究院 | Moisture/ultraviolet double-curing organic silicon adhesive |
| CN105524589B (en) * | 2016-01-18 | 2018-12-18 | 矽时代材料科技股份有限公司 | A kind of Liquid optical clear adhesive stick and preparation method thereof |
| CN106433453A (en) * | 2016-10-25 | 2017-02-22 | 北京化工大学 | Ultraviolet-moisture dual-curing solvent-free anti-pollution flashover coating |
| CN106883653A (en) * | 2017-03-21 | 2017-06-23 | 江门市凌云涂料有限公司 | A kind of ultraviolet moisture dual cure three-proofing coatings of LED and preparation method thereof |
| CN109929079A (en) * | 2019-02-27 | 2019-06-25 | 惠州市德佑威新材料有限公司 | A kind of UV/ moisture dual cure resin and preparation method thereof |
| CN111040726A (en) * | 2019-12-26 | 2020-04-21 | 烟台德邦科技有限公司 | UV (ultraviolet) moisture dual-curing organic silicon coating adhesive |
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